JP5736633B2 - Catalyst and production method thereof - Google Patents

Catalyst and production method thereof Download PDF

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JP5736633B2
JP5736633B2 JP2009038276A JP2009038276A JP5736633B2 JP 5736633 B2 JP5736633 B2 JP 5736633B2 JP 2009038276 A JP2009038276 A JP 2009038276A JP 2009038276 A JP2009038276 A JP 2009038276A JP 5736633 B2 JP5736633 B2 JP 5736633B2
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catalyst
slurry
method
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metallosilicate
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JP2009274061A (en
JP2009274061A5 (en
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琢弥 畑岸
琢弥 畑岸
知弘 山田
知弘 山田
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株式会社明電舎
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26DRYING
    • F26BDRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B3/00Drying solid materials or objects by processes involving the application of heat
    • F26B3/02Drying solid materials or objects by processes involving the application of heat by convection, i.e. heat being conveyed from a heat source to the materials or objects to be dried by a gas or vapour, e.g. air
    • F26B3/10Drying solid materials or objects by processes involving the application of heat by convection, i.e. heat being conveyed from a heat source to the materials or objects to be dried by a gas or vapour, e.g. air the gas or vapour carrying the materials or objects to be dried with it
    • F26B3/12Drying solid materials or objects by processes involving the application of heat by convection, i.e. heat being conveyed from a heat source to the materials or objects to be dried by a gas or vapour, e.g. air the gas or vapour carrying the materials or objects to be dried with it in the form of a spray, i.e. sprayed or dispersed emulsions or suspensions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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    • B01J29/076Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027Powdering
    • B01J37/0036Grinding
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
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    • B01J2229/10After treatment, characterised by the effect to be obtained
    • B01J2229/18After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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    • B01J29/16Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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    • B01J29/00Catalysts comprising molecular sieves
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    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • C07C2529/82Phosphates
    • C07C2529/83Aluminophosphates (APO compounds)
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    • C07C2529/89Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/58Recycling
    • Y02P20/588Recycling involving immobilised starting materials, reagents or catalysts

Description

  The present invention relates to advanced utilization of natural gas, biogas, and methane hydrate mainly composed of methane. Natural gas, biogas, and methane hydrate are considered to be the most effective energy resources as a countermeasure against global warming, and interest in utilization technology is increasing. Taking advantage of its cleanliness, methane resources are attracting attention as the next generation of new organic resources and hydrogen resources for fuel cells. The present invention relates to a catalytic chemical conversion technique and a catalyst production method for efficiently producing an aromatic compound mainly composed of benzene and naphthalene as raw materials for chemical products such as plastics and high-purity hydrogen gas from methane.

  As a method of producing an aromatic compound such as benzene and hydrogen from methane, a method of reacting methane in the presence of a catalyst is known. As the catalyst at this time, molybdenum supported on ZSM-5-based zeolite is effective (Non-patent Document 1, Patent Document 1, and Patent Document 2). However, even when these catalysts are used, there are problems that carbon deposition is large and catalyst performance deteriorates in a short time due to carbon deposition and that the conversion rate of methane is low.

  In order to improve this problem, it has been studied to make the catalyst shape into a pellet type that can be used in a fixed bed type reaction facility, and to increase the proportion of the catalyst component contained in the pellet and to react efficiently with methane. . However, in the case of the fixed bed reaction method, 10% or more of inorganic and organic binders are indispensable from the viewpoint of mechanical strength, and there is a problem because the dimensions are limited to millimeters or more.

  Although the catalyst of the particle shape applicable to the fluidized bed type reaction equipment as shown in patent document 3 is also devised, the ratio of the catalyst component present in the particles from the viewpoint of wear resistance and impact resistance is 50% or less, which is inferior to the fixed-bed pellet type with mechanical strength adjustment. Further, since the catalyst is deactivated in a short time, it is essential to regenerate the catalyst.

JOURNAL OF CATALYSIS, 1997, pp. 165, pp. 150-161

JP 10-272366 A Japanese Patent Laid-Open No. 11-60514 JP-A 61-266306

  In order to improve the conversion rate of methane, it is essential to improve the contact efficiency between the reaction gas and the catalyst, and the shape of the catalyst also greatly affects the reaction process. The shape is roughly classified into a pellet type molded body for a fixed bed and a granulated body for a fluidized bed and a moving bed. Pellet-type molded products require materials other than the catalyst required at the time of molding, such as organic binders, inorganic binders, glass fibers, pore formers, etc., and consider the effects of these additives on the catalyst. There is a need to.

  In the case of a granulated product, the particle diameter is as small as several tens to several hundreds of microns, and there is an advantage that the contact efficiency with the reaction gas is increased. It is an absolute requirement to have excellent heat resistance and thermal shock resistance. In order to satisfy these requirements, a large number of binders must be mixed or coated on the granulated material in addition to the catalyst material. In particular, according to Patent Document 3, when only the raw material zeolite powder slurry is spray-dried, a catalyst granule having a temporary spherical shape can be obtained, but it is easily broken by operation such as transportation and vibration. In addition to the zeolite powder, a suitable binder must be incorporated.

Therefore, a catalyst production method for solving the above-mentioned problems is a catalyst production method for performing a lower hydrocarbon aromatization reaction, which is a metallo having 4.5 to 6.5 angstrom diameter pores. At least selected from rhenium, vanadium, molybdenum, tungsten, chromium and compounds thereof in a slurry containing catalyst powder composed of particles having a cumulative frequency of 50% and 1.0 μm or less obtained by refining a metallosilicate-containing raw material containing silicate One or more kinds of metal components are added, and the slurry is dried by a spray drying method to obtain a granulated product of the catalyst in which the metal components are supported on the metallosilicate.

  Moreover, the catalyst for solving the said subject is a catalyst which consists of the said manufacturing method.

The metallosilicate raw material may be refined by a bead mill. The supported amount of molybdenum is preferably 2 to 12% by weight with respect to the total amount of the catalyst powder. The slurry may be dried by spray drying after aging. Examples of the aging include standing in an air atmosphere at normal temperature and pressure. Furthermore, you may add polyvinyl alcohol (henceforth PVA) to the said slurry.

  According to the method for producing a catalyst according to the above invention, it is possible to provide a catalyst in which the effective area of the crystal surface portion of the catalyst is increased and the crushing strength of the catalyst granule is improved without using a binder.

The SEM photograph of the granulated body of Example 1 (acceleration voltage 15.0 kV, magnification 1000 times). The SEM photograph of the granulated body of Example 1 (acceleration voltage 15.0 kV, magnification 20000 times). The SEM photograph of the granulated body of Example 2 (acceleration voltage 15.0 kV, magnification 1000 times). The SEM photograph of the granulated body of Example 2 (acceleration voltage 15.0 kV, magnification 20000 times). The SEM photograph of the granulated body of Example 4 (acceleration voltage 15.0 kV, magnification 1000 times). The SEM photograph of the granulated body of Example 4 (acceleration voltage 15.0 kV, magnification 5000 times). The SEM photograph (1000-times multiplication factor) which showed distribution of the element (O, Al, Si, Mo) in the surface of the granulated body of Example 4. FIG. The SEM photograph (10,000 times magnification) which showed distribution of the element (O, Al, Si, Mo) in the surface of the granulation body of Example 4. FIG. The SEM photograph of the granulated body of Example 5 (acceleration voltage 15.0 kV, magnification 1000 times). The SEM photograph of the granulated body of Example 5 (acceleration voltage 15.0 kV, magnification 5500 times). The SEM photograph (10,000 times magnification) which showed distribution of the element (O, Al, Si, Mo) in the surface of the granulated body of Example 5. FIG.

  In the catalyst production method according to the invention, a metallosilicate-containing raw material is refined and highly dispersed by a bead mill, and is converted to a granulated body by spray drying immediately after slurry preparation or after aging for a certain period of time. The aging may be performed by allowing the slurry to stand under an air atmosphere at normal temperature and pressure.

(1) Catalyst carrier The metallosilicate-containing raw material contains at least one metal component selected from rhenium, vanadium, molybdenum, tungsten, chromium and compounds thereof as a catalyst material, and is substantially as a carrier supporting this catalyst material. And metallosilicates having pores with a diameter of 4.5 to 6.5 angstroms. The metallosilicate is exemplified in JP-A No. 2004-97891. Specifically, as a metallosilicate (porous metallosilicate), for example, in the case of an aluminosilicate, a molecular sieve 5A composed of silica and alumina, a fossite (NaY and NaX), ZSM-5, MCM- 22 is mentioned. Further, it is a porous body mainly composed of phosphoric acid and is composed of 6-13 angstrom micropores and channels such as ALPO-5 and VPI-5, and partly composed mainly of silica. Examples thereof include mesoporous porous carriers such as FSM-16 and MCM-41 characterized by cylindrical pores (channels) having mesopores (10 to 1000 angstroms) containing alumina as a component. Furthermore, in addition to the alumina silicate, a metallosilicate composed of silica and titania can be used as a catalyst.

(2) Loading of supported metal on catalyst carrier A method of impregnating and supporting a predetermined concentration of molybdenum on a metallosilicate as a carrier is preferable. The supported amount of molybdenum is preferably 2 to 12% by weight based on the total amount of the catalyst after calcination.

  Moreover, it is good to add PVA to the said slurry. When a granulated product obtained by drying slurry containing catalyst powder refined by a bead mill by spray drying is used, gas is generated in the granulated product during firing, and spherical particles are ruptured. A phenomenon occurs in which particles are defective. Therefore, when PVA is added, many fine holes can be formed in the granulated body by vaporizing and removing PVA during firing. The sudden escape can be prevented by preventing the gas from escaping from the pores, so that no defect can occur. The addition amount of the PVA is preferably 0.1 to 1% by weight with respect to the metallosilicate in the slurry.

(3) Refinement of catalyst powder A method for preparing a slurry in which a metallosilicate raw material or a metallosilicate supporting the metal component is refined to 1 micron or less by a bead mill will be described. For example, catalyst powder: water = 1: 4 is weighed with respect to water in which the metallosilicate raw material or the metallosilicate carrying the metal component (hereinafter referred to as catalyst powder) is used as a slurry solution. The mixing ratio is not limited to this, and it is preferable to adjust appropriately according to the physical properties of the metallosilicate to be used. In this case, the slurry viscosity is preferably 100 cps or less. When the catalyst powder and water are mixed, the catalyst powder is adjusted to about 0.4 to 1 kg / min and charged in a state where the whole amount of water is previously charged in the mixer and stirred. If it is earlier, the catalyst powder aggregates and settles in the mixer, which is not preferable. In this case, a mixer whose blade shape and rotation speed can be arbitrarily set is used. In particular, the wing shape and the rotation speed are not limited.

  The pulverizing beads used in the bead mill are preferably zirconia.

  Using a bead mill having the above specifications, a hose pump for circulating the slurry is started to refine the catalyst powder. Refinement can be adjusted with bead diameter and time. The metallosilicate raw material may be refined by a bead mill so that the particle size of the metallosilicate is 50 μm or less and 1.0 μm or less. For example, in the case of a ZSM-5 raw material having an average particle diameter of 42 μm, it can be refined to 0.3 μm in one hour of pulverization time. The slurry obtained by refining the catalyst powder is recovered by switching the supply line from the closed system to the open system.

(4) Granulation A method for drying and granulating the catalyst powder in the slurry with a spray dryer will be described. The slurry prepared in (3) is preferably dried and granulated directly by a spray drying apparatus or used after aging for a certain time (for example, 6 days). The type of the spray dryer is not particularly limited, but the downward spray co-current system is preferable. The nozzle is preferably a two-fluid nozzle system, and the orifice diameter is preferably changed as appropriate depending on the viscosity of the slurry and the particle shape of the catalyst powder. The operating conditions of the spray dryer are appropriately adjusted depending on the slurry viscosity and the particle size of the catalyst powder in the slurry. The operating conditions are not particularly limited.

  According to the method for producing a catalyst according to the present invention, the effective area of the crystal surface of the catalyst is increased by refining the nano-sized catalyst powder, and the crushing strength of the catalyst granule is improved without adding a binder. Catalyst can be provided. Therefore, it is possible to easily produce spherical particles that were difficult with the rolling granulation method. In addition, the inorganic binder is unnecessary or significantly reduced, and the metal is easily supported on the catalyst powder contained in the granulated body.

  Furthermore, by adding the metal component to the refined catalyst powder-containing slurry and impregnating the catalyst powder with the metal component, uniform metal loading on the catalyst powder is facilitated and the fluidity of the granulated body is excellent. A catalyst with improved crushing strength can be provided. And the crushing strength of a granulated body becomes still higher because PVA is added to the slurry.

  Examples and comparative examples according to the invention are shown below.

(Comparative Example 1)
As the catalyst powder according to Comparative Example 1, proton type ZSM-5 which is a kind of metallosilicate having an average particle diameter of 31 μm and a crystal diameter of 0.08 μm was used. The particle diameter and crystal diameter were measured by calculating the average value of particles arbitrarily selected from an electron micrograph. The slurry was prepared using purified water as a solvent so that the solid content concentration of the catalyst powder raw material was 20% by weight.

And after stirring this slurry for 1 hour, it granulated with the spray-dry apparatus (The Yamato Scientific Co., Ltd. make, model DL-41). The operating conditions were set to an inlet temperature of 230 to 240 ° C. and an outlet temperature of 90 ° C., and then dried and granulated with a dry air amount of 0.8 m 3 / min, a nozzle spray air pressure of 0.1 MPa, and a slurry feed amount of 20 g / min. The obtained granule was dried in air at 120 ° C. for 20 hours. About the intensity | strength of the granulated body, the crushing intensity | strength of each particle | grain was measured based on JISZ8841. The crushing strength of 15 obtained granules was measured. As shown in Table 3, all the granules were less than 0.06 gf / mm 2, which is the measurement limit value of the measuring machine.

Example 1
As the catalyst powder according to Example 1, one kind of metallosilicate ZSM-5 having an average particle diameter of 42 μm and a crystal diameter of 5 μm was used. The catalyst powder raw material was ammonia type, and it was calcined at a predetermined temperature and converted to proton type. Metal loading was not performed for ZSM-5 used in this example.

  First, a method for refining catalyst powder using a bead mill will be described. 4 kg of purified water was weighed with respect to 1 kg of catalyst powder, and the entire amount of purified water was put into a stirring vessel. While rotating the blades of the stirrer, the entire amount of catalyst powder was charged at 400 g / min, the slurry circulation pump was started, and the circulation and pulverization of the slurry was started. A part of the slurry was withdrawn every 15 minutes after the start, and the slurry viscosity and the particle size distribution of the catalyst powder were measured. Table 1 shows changes with time in the particle size distribution of the catalyst powder. The circulating pump was stopped 1 hour after the start of grinding, and the slurry in the system was collected. The recovered slurry was 3.76 kg with respect to 5 kg of the charged slurry weight.

Next, a granulation method using a catalyst powder spray drying apparatus will be described. The previously prepared slurry was aged for 5 days. In the aging, the slurry was allowed to stand under an air atmosphere at normal temperature and pressure. Then, it stirred with the stirring container. After setting the inlet temperature to 230 to 240 ° C. and the outlet temperature to 90 ° C., the spray drying device (Yamato Scientific Co., Ltd.) was used under the conditions of a dry air flow rate of 0.8 m 3 / min, a nozzle spray air pressure of 0.1 MPa, and a slurry feed rate of 20 g / min. Drying and granulation were started according to company type DL-41). The obtained granulated body was dried in air at 120 ° C. for 20 hours. The SEM (scanning electron microscope) photograph after drying is shown in FIG. Table 3 shows the result of the crushing strength of the granulated body (10-point average value).

(Example 2)
As the catalyst powder according to Example 2, one kind of metallosilicate ZSM-5 having an average particle diameter of 39 μm and a crystal diameter of 4.2 μm was used. The subsequent preparation conditions are the same as in Example 1. Moreover, the particle size distribution change of the catalyst powder refined | miniaturized by the bead mill was shown in Table 2, and the SEM photograph of the granulated material by a spray-dry apparatus (made by Yamato Scientific Co., Ltd. model DL-41) was shown in FIG. Although not disclosed in Table 3, it was confirmed that the crushing strength of the granulated material according to Example 2 was almost equal to the crushing strength of the granulated material according to Example 1.

  From the results of Tables 1 and 2, it can be seen that uniform nano-level catalyst powder can be refined in a short time. Furthermore, a fine and spherical granule as shown in FIGS. 1 and 2 is obtained by spray drying the refined catalyst powder. Moreover, after aging the catalyst powder containing slurry refined | miniaturized by the bead mill rather than the catalyst powder of the comparative example 1 of the nanosize (crystal diameter 80nm) obtained by spray-drying a slurry simply from the result of Table 3. Higher crushing strength can be obtained with the spray-dried granule of Example 1. Furthermore, since the catalyst powder contained in the granulated body of Example 1 is refined and the area of the crystal surface is increased, the contact efficiency with the reaction gas is increased, and the granulated body of Example 1 can be used under a high flow rate condition such as a fluidized bed process. It has been shown that it can contribute to the reaction as an efficient catalyst granulation. It has also been confirmed that the crushing strength can be obtained if the metallosilicate raw material is refined by a bead mill so that the particle size of the metallosilicate is 1.0 μm or less, particularly 0.5 μm or less at a cumulative frequency of 50%.

(Example 3)
As the catalyst powder according to Example 3, one type of metallosilicate ZSM-5 having an average particle diameter of 42 μm and a crystal diameter of 5 μm was used. The catalyst powder raw material was ammonia type, and it was calcined at a predetermined temperature and converted to proton type. Metal loading was not performed for ZSM-5 used in this example.

  First, a method for refining catalyst powder using a bead mill will be described. 20 kg of purified water was weighed with respect to 5 kg of the catalyst powder, and the entire amount of purified water was put into a stirring vessel. While rotating the blades of the stirrer, the entire amount of catalyst powder was charged at 400 g / min, the slurry circulation pump was started, and the circulation and pulverization of the slurry was started. After 1 hour from the start of pulverization, the powder was finely pulverized to 0.2 μm and the circulation pump was stopped, and then the slurry in the system was collected. The recovered slurry was 18.9 kg with respect to the charged slurry weight of 25 kg.

Next, a granulation method using a catalyst powder spray drying apparatus will be described. The previously prepared slurry was aged for 5 days. In the aging, the slurry was allowed to stand under an air atmosphere at normal temperature and pressure. Then, it stirred with the stirring container. After setting the inlet temperature to 230 to 240 ° C. and the outlet temperature to 90 ° C., the spray drying device (Yamato Scientific Co., Ltd.) was used under the conditions of a dry air flow rate of 0.8 m 3 / min, a nozzle spray air pressure of 0.1 MPa, and a slurry feed rate of 20 g / min. Drying and granulation were started according to company type DL-41). The obtained granulated body was dried in air at 120 ° C. for 20 hours. Then, it baked at 550 degreeC for 5 hours.

About the intensity | strength of the obtained granulated body, the crushing strength of 15 granulated bodies was measured with the measuring method based on JISZ8841. The measurement results are shown in Table 4. The average crushing strength of the granulated body was 60.8 gf / mm 2 or less.

  About the fluidity | liquidity of the granulated body, it was based on the bulk density measuring method based on JISZ2504 and JISR6126 (The index of fluidity is obtained from the way of the bulk reduction by tapping). It measured based on the Kawakami-type tap density measuring method. The measurement results are shown in Table 5. The Kawakami liquidity index indicates that the smaller the value, the better the fluidity. The fluidity index of the granulation was 0.38.

Example 4
In the catalyst powder according to Example 4, molybdenum is supported as a metal component on the metasilicate. In addition, the manufacturing method of the catalyst of a present Example is the same as the manufacturing method of the catalyst which concerns on Example 3 except having a procedure which impregnates and carries a metal component on the catalyst powder refined | miniaturized by the bead mill.

  First, a method for impregnating and supporting a supported metal after the catalyst powder is refined by a bead mill will be described. 2 kg of the slurry prepared under the same conditions as in Example 3 was aged for 5 days, and then stirred in a stirring vessel. Then, an aqueous solution in which 42 g of ammonium molybdate was dissolved in 200 g of water was added to this slurry, and the mixture was stirred for 3 hours.

Next, a granulation method using a catalyst powder spray drying apparatus will be described. After the slurry prepared above is set to an inlet temperature of 230 to 240 ° C. and an outlet temperature of 90 ° C., it is spray dried under the conditions of a dry air flow rate of 0.8 m 3 / min, a nozzle spray air pressure of 0.1 MPa, and a slurry feed rate of 20 g / min. Drying and granulation were started by an apparatus (manufactured by Yamato Scientific Co., Ltd., model DL-41). The obtained granulated body was dried in air at 120 ° C. for 20 hours. Then, it baked at 550 degreeC for 5 hours.

  Table 4 shows the results of the crushing strength (10-point average value) of the granulated material, and Table 5 shows the results of the fluidity index. The crushing strength and fluidity index were measured in the same manner as in Example 3. Moreover, the SEM photograph of the granulated body after baking is shown in FIG. 5 (1000 times magnification) and FIG. 6 (5000 times magnification). Further, SEM photographs showing the distribution of elements (O, Al, Si, Mo) on the surface of the granulated body are shown in FIG. 7 (magnification 1000 times) and FIG. 8 (magnification 10000 times).

(Example 5)
The method for producing the catalyst of this example is the same as the method for producing the catalyst according to Example 4 except that the method further includes adding a PVA aqueous solution to the slurry charged with the aqueous ammonium molybdate solution.

  That is, 2 kg of the slurry prepared under the same conditions as in Example 3 was aged for 5 days and then stirred in a stirring vessel. Then, an aqueous solution in which 42 g of ammonium molybdate was dissolved in 200 g of water was put into this slurry. Furthermore, 8 g of 10% PVA aqueous solution was added and stirred for 3 hours. The subsequent granulation method is the same as the granulation procedure of the catalyst according to Example 4.

  Table 4 shows the results of the crushing strength (10-point average value) of the granulated material, and Table 5 shows the results of the fluidity index. The crushing strength and fluidity index were measured in the same manner as in Example 3. Moreover, the SEM photograph of the granulated body after baking was shown in FIG. 9 (1000 times magnification) and FIG. 10 (5500 times magnification). Furthermore, the SEM photograph (10,000 times magnification) which showed distribution of the element (O, Al, Si, Mo) in the surface of a granule was shown in FIG.

  From the results of Table 4, the granule of Example 4 obtained by impregnating and supporting molybdenum in the slurry, spray drying and firing, rather than spray drying and firing the nano-sized raw material slurry as in Example 3. It can be seen that has a high crushing strength. Furthermore, it turns out that the granulated body of Example 5 obtained by adding PVA, spray drying, and baking has higher crushing strength.

  According to the results in Table 5, it can be seen that the catalysts of Examples 4 and 5 are granulates having excellent fluidity because the fluidity index is smaller than that of Example 3.

  In the granulated body of Example 4, a dense and spherical granulated body is obtained as shown in FIGS. Furthermore, according to the method for producing a catalyst according to Example 5 to which PVA was added, it was confirmed that a granulated body having few defects (dents) was obtained as shown in FIGS. Since the catalyst powder in the granulated body increases the area of the crystal surface by miniaturization, the contact efficiency with the reaction gas increases, and the catalyst is efficient even for reactions under high flow rate conditions such as a fluidized bed process. It can contribute as a granulated body.

In the element distribution photographs of FIGS. 7, 8, and 11, the photograph “O Ka1” indicates the distribution of oxygen. The photograph of “Al Ka1” shows the distribution of aluminum. The photograph of “Si Ka1” shows the distribution of silicon. The photograph “Mo La1” shows the distribution of molybdenum. The white part of the photo shows the distribution of elements. According to the above photograph, it can be confirmed that the metal element components (Al, Mo) are supported in a uniformly distributed state on the surface of the granulated body. The main components of the zeolite used in the examples are AlO 3 and SiO 2 , and the SiO 2 / Al 2 O 3 ratio of the main raw material is 40, so it is confirmed that Si is densely distributed on one side. it can.

  As is apparent from the results of the above examples, according to the catalyst production method of the present invention, the effective area of the crystal surface portion of the catalyst increases due to the refinement of the nano-sized catalyst powder by the bead mill. Further, it becomes possible to easily produce spherical particles, which was difficult with the rolling granulation method. Furthermore, an inorganic binder is unnecessary or can be greatly reduced. And the metal component illustrated by molybdenum is added to the slurry containing the refined catalyst powder so that the catalyst powder is impregnated with the metal component so that the catalyst powder contained in the granule is uniform. Metal loading becomes easy. Furthermore, the fluidity of the granulated body can be improved. Furthermore, the crushing strength of the granulated body is increased. In particular, the crushing strength can be further increased by adding PVA.

Claims (8)

  1. A method for producing a catalyst for performing an aromatization reaction of a lower hydrocarbon, comprising:
    Rhenium in a slurry containing catalyst powder composed of particles having a cumulative frequency of 50% and 1.0 μm or less obtained by refining a metallosilicate-containing raw material containing a metallosilicate having pores having a diameter of 4.5 to 6.5 angstroms , Granulation of a catalyst in which at least one metal component selected from vanadium, molybdenum, tungsten, chromium and a compound thereof is added, and the slurry is dried by a spray drying method and the metal component is supported on the metallosilicate. A method for producing a catalyst, comprising obtaining a body.
  2. The method for producing a catalyst according to claim 1, wherein the miniaturization is performed by a bead mill.
  3. The method for producing a catalyst according to claim 1 or 2, wherein the slurry is aged by spray drying after aging.
  4. The method for producing a catalyst according to claim 3, wherein the aging is performed by allowing the slurry to stand under an air atmosphere at normal temperature and pressure.
  5. The method for producing a catalyst according to any one of claims 1 to 4 , wherein the supported amount of molybdenum is 2 to 12% by weight with respect to the total amount of the catalyst powder.
  6. The method for producing a catalyst according to any one of claims 1 to 5 , wherein polyvinyl alcohol is added to the slurry.
  7. The method for producing a catalyst according to any one of claims 1 to 6 , wherein the catalyst is a catalyst for producing an aromatic compound and hydrogen from a lower hydrocarbon.
  8. A catalyst comprising the production method according to any one of claims 1 to 7 .
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